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1
Temperature-Controlled Redox-Neutral Ruthenium(II)-Catalyzed
Regioselective Allylation of Benzamides with Allylic Acetates
Rajendran Manikandan and Masilamani Jeganmohan*
Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008,
India
Email: mjeganmohan@iiserpune.ac.in
Supporting Information (SI)
Table of Contents
S2 – S3 Experimental Section
S4 – S5 Optimization Studies
S6 – S30 Spectral Data of all Compounds
S31 – S41 Mechanistic Studies (deuterium studies, temperature studies and DFT
calculation)
S42 – S114 Copies of 1H and
13C NMR Spectra of All Compounds.
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016
2
Experimental Section
General Procedure for the Allylation of Aromatic amides with Allylic Acetates
Catalyzed by a Ruthenium Complex
A 15-mL pressure tube with septum containing amide 1 (100 mg), [{RuCl2(p-cymene)}2]
(5.0 mol %) and AgSbF6 (20 mol %) was evacuated and purged with nitrogen gas three times
(AgSbF6 was taken inside the glove box). To the tube, was then added 1,2-dichloroethane
(1.0 mL) via syringe. After that, allylic acetate 2 (2.0-2.5 equiv) and 1,2-dichloroethane (2.0
mL) were added via syringes and again the reaction mixture was evacuated and purged with
nitrogen gas three times. After that, the septum was taken out and immediately a screw cap
was used to cover the tube. Then, the reaction mixture was allowed to stir at rt for 16-36 h.
Then, the reaction mixture was diluted with CH2Cl2, filtered through Celite and silica gel, and
the filtrate was concentrated. The crude residue was purified through a silica gel column
using petroleum ether and ethyl acetate (for some compounds CH2Cl2 and MeOH
combination were used. It has been mentioned in the substrates below) as eluent to give pure
3.
Note: Liquid amide reactants are added after adding 1.0 mL of solvent. For product 3aa, 2.0
equiv of allyl acetate (2a) was used.
General Procedure for the Alkenylation of Aromatic amides with Allylic Acetates
catalyzed by Ruthenium Complex.
A 15-mL pressure tube with septum containing amide 1 (100 mg), [{RuCl2(p-cymene)}2]
(5.0 mol %) and AgSbF6 (20 mol %) was evacuated and purged with nitrogen gas three times
(AgSbF6 was taken inside the glove box). To the tube, was then added 1,2-dichloroethane
(1.0 mL) via syringe. After that, allylacetate 2a (1.2-2.0 equiv) and 1,2-dichloroethane (2.0
mL) were added via syringes and again the reaction mixture was evacuated and purged with
nitrogen gas three times. After that, the septum was taken out and immediately a screw cap
was used to cover the tube. Then, the reaction mixture was allowed to stir at 100-120 °C for
12-20 h. Then, the reaction mixture was diluted with CH2Cl2, filtered through Celite and
silica gel, and the filtrate was concentrated. The crude residue was purified through a silica
gel column using petroleum ether and ethyl acetate as eluent (for some compounds CH2Cl2
and MeOH combination were used. It has been mentioned in the substrates below) to give
pure 4.
3
Note: For products 4ba-4ga, 1.2 equiv of allylacetate (2a) and products 4ja-4qa, 2.0 equiv of
allylacetate (2a) was used. Reaction temperature is 120 °C for products 4fa, 4ga, 4la, 4ma,
4na and 4pa.
General Procedure for the Synthesis of Isochromanone Derivatives.
ortho Allylated aromatic amides (3) (50 mg) was taken in a 10-mL sealed tube and dissolved
with 0.5 mL of 1,4 dioxane and 2.0 mL of 6N HCl. Then, the reaction mixture heated at
110°C for 12 h. After cooling to ambient temperature, water was poured into the reaction
mixture and extracted with ethyl acetate. The organic layer was washed with brine solution
and dried over Na2SO4. The solution was concentrated under the reduced pressure. The crude
residue was purified through a silica gel column using petroleum ether and ethyl acetate as
eluent to give pure 5.
General Procedure for the Synthesis of Isobenzofuranone Derivatives.
ortho Vinylated aromatic amides (4) (50 mg) was taken in a 10-mL sealed tube and dissolved
with 0.5 mL of 1,4-dioxane and 2.0 mL of 6N HCl. Then the reaction mixture heated at
120°C for 12 h. After cooling to ambient temperature, water was poured in to the reaction
mixture and extracted with ethyl acetate. The organic layer was washed with brine solution
and dried over Na2SO4. The solution was concentrated under the reduced pressure. The crude
residue was purified through a silica gel column using petroleum ether and ethyl acetate as
eluent to give pure 6.
4
Table S1. Optimization Studiesa
Entry Solvent Allyl source Additive Yield of 3aa
(%)b
1 Iso-propanol Allyl acetate (2.0equiv) AgSbF6 38
2 Methanol Allyl acetate (2.0equiv) AgSbF6 44
3 THF Allyl acetate (2.0equiv) AgSbF6 68
4 DME Allyl acetate (2.0equiv) AgSbF6 66
5 DMF Allyl acetate (2.0equiv) AgSbF6 NR
6 DMSO Allyl acetate (2.0 equiv) AgSbF6 NR
4 Toluene Allyl acetate (2.0 equiv) AgSbF6 NR
8 1,4 Dioxane Allyl acetate (2.0 equiv) AgSbF6 50
9 CH3CN Allyl acetate (2.0 equiv) AgSbF6 NR
10 ClCH2CH2Cl Allyl acetate (2.0 equiv) AgSbF6 81
11 ClCH2CH2Cl Allyl acetate (2.0 equiv) AgOTf 71
12 ClCH2CH2Cl Allyl acetate (2.0 equiv) AgBF4 69
13 ClCH2CH2Cl Allyl acetate (2.0 equiv) KPF6 NR
14 ClCH2CH2Cl Allyl bromide (2.0 equiv) AgSbF6 NR
15 ClCH2CH2Cl Allyl carbonate (2.0 equiv) AgSbF6 NR
16 ClCH2CH2Cl Allyl alcohol (2.0 equiv) AgSbF6 NR
aAll reactions were carried out under the following conditions: 1a (100 mg), 2a (2.0equiv),
[{RuCl2(p-cymene)}2] (5mol %), additive (20 mol %) andsolvent (3.0 mL) at rt for 16 h under
the N2 atmosphere. b Isolated yield.
Note: The catalytic reaction was tried without ruthenium and AgSbF6. No product 3aa was
observed in the reaction.
Initially, the allylation reaction was screened with various additives, solvents and allyl
sources. The allylation reaction of 1a with 2a was tried in the presence of [{RuCl2(p-
cymene)}2] (5.0 mol %) and AgSbF6 (20 mol %) in various solvents such as iso-PrOH,
MeOH, 1,4-dioxane, THF, DME, ClCH2CH2Cl, methanol, toluene, CH3CN, DMSO, DMF
and water at room temperature for 16 h (entries 1-10). Among them, ClCH2CH2Cl was very
effective, yielding product 3aa in 81% yield (entry 10). iso-PrOH, MeOH, THF, DME and
1,4-dioxane were partially effective, providing product 3aa in 38%, 44%, 68%, 66% and 50%
yields, respectively. Remaining solvents were not effective. Further, the allylation reaction
5
was examined with various additives such as AgSbF6, AgBF4, AgOTf, KPF6 and CuBF4
(entries 10-13) Among them, AgSbF6 was effective, affording product 3aa in 81% yield.
AgBF4 and AgOTf were partially effective, providing product 3aa in 69% and 71% yields,
respectively. KPF6 and CuBF4 were not effective. The catalytic reaction was also tested with
other allyl sources such as allyl bromide, allyl alcohol and allyl carbonate. However, in these
reactions, no allylated product 3aa was observed (entries 14-16).
We have tried the ortho alkenylation of 4-methoxy-N-methylbenzamide (1h) with allyl
acetate (2a) in the presence of a catalytic amount of Ru(OAc)2(p-cymene) (10 mol %),
AgSbF6 (20 mol %) in ClCH2CH2Cl at room temperature for 36 h. In the reaction, the
expected ortho alkenylated benzamide 3ha was observed in 52% yield. But, the same
reaction does not proceed without AgSbF6. This result clearly reveals that the AgSbF6 is
crucial for the reaction. In the reaction, AgSbF6 acts as a halogen scavenger as well as
forming the active cationic ruthenium species 8 for the catalytic reaction.
6
Spectral Data of All Compounds.
(4-Allylbenzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3aa).
The representative general procedure was followed using 1a (100 mg), 2a (2.0 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 96 mg and yield is 81%.
Colorless solid; eluent (30% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): 6.66 (d, J = 8.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 1H), 5.91 (s,
2H), 5.89 – 5.77 (m, 1H), 4.98 (dq, J = 16.0, 4.0 Hz, 1H), 4.93 (dt, J = 12.0, 4.0 Hz, 1H),
3.53 (t, J= 8.0 Hz, 2H), 3.36 (d, J = 8.0 Hz, 2H), 3.12 (t, J = 8.0 Hz, 2H), 1.87 (p, J = 8.0 Hz,
2H), 1.75 (p, J = 8.0 Hz, 2H).
13C NMR (CDCl3, 100 MHz): 168.9, 147.3, 146.2, 135.2, 131.8, 119.7, 118.6, 115.5, 106.3,
100.9, 48.9, 45.4, 30.9, 25.9, 24.5.
HRMS (ESI): calc. for [(C15H17NO3)H] (M+H) 260.1287, measured 260.1289.
IR (ATR)ṽ (cm-1
): 3011, 2931, 2817, 1651, 1425, 1317, 1049, 918, 871, 668.
Rf (hexane/ethyl acetate = 70:30): 0.23.
(2-Allyl-4-methoxyphenyl)(pyrrolidin-1-yl)methanone (3ba).
The representative general procedure was followed using 1b (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 85 mg and yield is 71%.
Colorless solid; eluent (28% ethylacetate in hexane).
7
1H NMR (CDCl3, 400 MHz): 7.10 (d, J = 8.0Hz, 1H),6.74 (d, J = 4.0Hz, 1H),6.71 (dd, J =
8.0, 4.0 Hz, 1H),5.90 -5.80 (m, 1H), 5.06 – 4.97 (m, 2H), 3.76 (s, 3H), 3.57 (t, J = 8.0Hz,2H),
3.34 (d, J = 8.0Hz, 2H), 3.11 (d, J = 8.0Hz, 2H), 1.88 (p, J = 4.0Hz, 2H), 1.79 (p, J = 4.0Hz,
2 H).
13C NMR (CDCl3, 100 MHz): 169.7, 159.8, 138.3, 136.5, 130.2, 127.4, 115.9, 115.3, 111.3,
55.2, 48.8, 45.4, 37.5, 25.9, 24.5.
HRMS (ESI): calc. for [(C15H19NO2)H] (M+H) 246.1494, measured 246.1502.
IR (ATR)ṽ (cm-1
): 2978, 2901, 1614, 1579, 1468, 1219, 1031, 858, 744, 598.
Rf (hexane/ethyl acetate = 70:30): 0.31.
(2-Allyl-4-methylphenyl)(pyrrolidin-1-yl)methanone (3ca).
The representative general procedure was followed using 1c (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 76 mg and yield is 63%.
Colorless solid; eluent (30% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): 7.06 (d, J = 8.0 Hz, 1H), 7.02 (s, 1H), 6.99 (d, J = 8.0 Hz,
1H), 5.91 – 5.81 (m, 1H), 5.02 (dq, J = 16.0, 4.0 Hz, 1H), 4.98 (dq, J = 8.0, 4.0 Hz, 1H), 3.58
(t, J = 8.0 Hz, 2H), 3.37 (d, J = 8.0 Hz, 2H), 3.10 (t, J = 8.0 Hz, 2H), 2.29 (s, 3H), 1.90 (p, J
= 8.0 Hz, 2H), 1.79 (p, J = 8.0 Hz, 2H).
13C NMR (CDCl3, 100 MHz): 169.8, 138.7, 136.9, 136.1, 134.8, 130.4, 126.8, 125.9, 115.7,
48.7, 45.3, 37.3, 25.9, 24.5, 21.2.
HRMS (ESI): calc. for [(C15H19NO)H] (M+H) 230.1545, measured 230.1553.
IR (ATR)ṽ (cm-1
): 2931, 2817, 1727, 1637, 1435, 1312, 1041, 908, 875, 661.
Rf (hexane/ethyl acetate = 70:30): 0.38.
8
(2-Allylphenyl)(pyrrolidin-1-yl)methanone (3da).
The representative general procedure was followed using 1d (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 85 mg and yield is 69%.
Colorless solid; eluent (30% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): 7.31 (td, J = 8.0, 4.0 Hz, 1H), 7.26 (d, J = 8.0 Hz, 1H), 7.21
(td, J = 8.0, 4.0 Hz, 2H),5.94 -5.86 (m, 1H), 5.09 – 5.01 (m, 2H), 3.63 (t, J = 8.0Hz,2H), 3.44
(d, J = 8.0Hz,2H), 3.14 (t, J = 8.0Hz,2H), 1.94 (p, J = 4.0Hz,2H), 1.84 (p, J = 4.0Hz,2 H).
13C NMR (CDCl3, 100 MHz): 168.6, 138.7, 136.4, 135.7, 132.8, 129.4, 127.5,122.9,
116.7,48.7, 45.5, 37.1, 25.9, 24.5.
HRMS (ESI): calc. for [(C14H17NO)H] (M+H) 216.1388, measured 216.1395.
IR (ATR)ṽ (cm-1
): 2979, 1614, 1570, 1413, 1261, 1048, 879, 717, 628.
Rf (hexane/ethyl acetate = 70:30): 0.31.
(2-Allyl-4-bromophenyl)(pyrrolidin-1-yl)methanone (3ea).
The representative general procedure was followed using 1e (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 77 mg and yield is 66%.
Colorless solid; eluent (24% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.38 (d, J = 4.0Hz,1H),7.34 (dd, J = 8.0, 4.0 Hz,1H),7.05 (d,
J = 8.0Hz,1H),5.88 -5.78 (m, 1H), 5.08 – 5.02 (m, 2H), 3.58 (t, J = 8.0Hz,2H), 3.37 (d, J =
8.0Hz,2H), 3.09 (t, J = 8.0Hz,2H), 1.90 (p, J = 4.0Hz,2H), 1.81 (p, J = 4.0Hz,2H).
9
13C NMR (CDCl3, 100 MHz): 169.6, 137.5, 136.7, 136.1, 129.8, 128.9, 126.2, 125.9, 115.8,
48.7, 45.3, 37.4, 25.9, 24.5.
HRMS (ESI): calc. for [(C14H16BrNO)H] (M+H) 294.0494, measured 294.0495.
IR (ATR)ṽ (cm-1
): 3078, 2931, 1634, 1589, 1463, 1259, 1041, 874, 747, 668.
Rf (hexane/ethyl acetate = 70:30): 0.29.
(2-Allyl-4-chlorophenyl)(pyrrolidin-1-yl)methanone(3fa).
The representative general procedure was followed using 1f (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 73 mg and yield is 61%.
Colorless solid; eluent (30% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): 7.21 (d, J = 4.0 Hz, 1H), 7.17 (dd, J = 8.0, 4.0 Hz, 1H), 7.10
(d, J = 8.0 Hz, 1H), 5.87 – 5.77 (m, 1H), 5.05 (dq, J = 12.0, 4.0 Hz, 1H), 5.02 (dq, J = 8.0,
4.0 Hz, 1H), 3.57 (t, J = 8.0 Hz, 2H), 3.37 (dd, J = 8.0, 4.0 Hz, 2H), 3.08 (t, J = 8.0 Hz, 2H),
1.90 (p, J = 8.0 Hz, 2H), 1.79 (p, J = 8.0 Hz, 2H).
13C NMR (CDCl3, 100 MHz): 168.5, 138.5, 135.9, 135.7, 134.6, 129.8, 127.3, 126.4, 116.7,
48.6, 45.4, 37.1, 25.9, 24.5.
HRMS (ESI): calc. for [(C14H16ClNO)H] (M+H) 250.0999, measured 250.1003.
Rf (hexane/ethyl acetate = 70:30): 0.31.
(2-Allyl-4-Fluorophenyl)(pyrrolidin-1-yl)methanone (3ga).
10
The representative general procedure was followed using 1g (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 62 mg and yield is 52%.
Colorless liquid; eluent (25% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): 7.16 (dd, J = 8.0, 4.0 Hz, 1H), 6.93 (dd, J = 8.0, 4.0 Hz, 1H),
6.89 (td, J = 8.0, 4.0 Hz, 1H), 5.88 – 5.79 (m, 1H), 5.06 (dq, J = 8.0, 4.0 Hz, 1H), 5.03 (dq, J
= 8.0, 4.0 Hz, 1H), 3.59 (t, J = 8.0 Hz, 2H), 3.39 (d, J = 8.0 Hz, 2H), 3.10 (t, J = 8.0 Hz, 2H),
1.91 (p, J = 8.0 Hz, 2H), 1.81 (p, J = 8.0 Hz, 2H).
13C NMR (CDCl3, 100 MHz): 168.9, 163.9, 161.5, 139.4 and 139.3 (F-coupling), 135.8,
133.6, 127.8 and 127.7 (F-coupling), 116.7 and 116.5(F-coupling), 113.3 and 113.1 (F-
coupling), 48.7, 45.5, 37.2, 25.9, 24.4.
HRMS (ESI): calc. for [(C14H16FNO)H] (M+H) 234.1294, measured 234.1299.
Rf (hexane/ethyl acetate = 70:30): 0.33.
2-Allyl-4-methoxy-N-methylbenzamide (3ha).
The representative general procedure was followed using 1h (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 63 mg and yield is 51%.
Colorless solid; eluent (30% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.33(d, J = 8.0Hz, 1H), 6.73 – 6.69 (m, 2H), 6.02 – 5.92 (m,
1H), 5.87 (s, 1H), 5.05 (dq, J = 8.0, 4.0 Hz, 1H), 5.0 (dq, J = 12.0, 4.0 Hz, 1H), 3.78 (s, 3H),
3.53 (d, J = 8.0 Hz, 2H), 2.91 (d, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 170.2, 160.7, 139.9, 137.5, 129.0, 128.9, 116.0, 115.9, 111.3,
55.2, 37.8, 26.6.
HRMS (ESI): calc. for [(C12H15NO2)H] (M+H) 206.1181, measured 206.1187.
IR (ATR)ṽ (cm-1
): 3289, 2922, 1630, 1536, 1403, 1157, 1041, 999.
11
2-Allyl-4-iodo-N-methylbenzamide(3ia).
The representative general procedure was followed using 1i (100 mg), 2a (2.5 equiv) and the
reaction was done at rt for 36 h. The desired product was isolated in 49 mg and yield is 42%.
Colorless solid; eluent (30% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.57 (d, J = 4.0Hz,1H), 7.54 (dd, J = 8.0, 4.0 Hz, 1H), 7.06
(d, J = 8.0Hz,1H),5.98 (s, 1H), 5.96 – 5.86 (m, 1H), 5.07 (dq, J = 8.0, 4.0 Hz, 1H), 4.99 (dq, J
= 12.0, 4.0 Hz, 1H), 3.44 (d, J = 8.0Hz,2H), 2.91 (d, J = 4.0Hz,3H).
13C NMR (CDCl3, 100 MHz): 169.7, 139.8, 139.2, 136.7, 135.9, 135.4, 128.7, 116.7, 96.3
37.1, 26.6.
HRMS (ESI): calc. for [(C11H12INO)H] (M+H) 302.0042, measured 302.0049.
(4-(But-2-en-1-yl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3ab).
The representative general procedure was followed using 1a (100 mg), 2b (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 98 mg and yield is 78%.
Colorless liquid; eluent (27% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): E isomer: 6.66 (d, J = 8.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 1H),
5.93 (s, 2H), 5.51 – 5.34 (m, 2H), 3.55 (t, J = 8.0 Hz, 2H), 3.37 (d, J= 8.0 Hz, 2H), 3.13 (t, J
= 8.0 Hz, 2H), 1.89 (p, J = 8.0 Hz, 2H), 1.78 (p, J = 8.0 Hz, 2H), 1.64 (d, J = 8.0 Hz, 3H).
Z isomer: 6.66 (d, J = 8.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 1H), 5.93 (s, 2H), 5.51 – 5.34 (m,
2H), 3.55 (t, J = 8.0 Hz, 2H), 3.29 (d, J = 4.0 Hz, 1H), 3.13 (t, J = 8.0 Hz, 2H), 1.89 (p, J =
8.0 Hz, 2H), 1.78 (p, J = 8.0 Hz, 2H), 1.58 (d, J = 4.0 Hz, 1H).
12
13C NMR (CDCl3, 100 MHz): E isomer: 169.2, 147.3, 146.1, 131.7, 127.7, 127.1, 126.3,
124.8, 106.2, 100.9, 48.9, 45.4, 29.8, 25.9, 24.6, 12.8. Z isomer: 169.1, 147.3, 146.1, 131.7,
127.7, 126.3, 119.8, 119.7, 106.2, 100.9, 48.9, 45.4, 29.6, 25.9, 24.6, 17.8.
HRMS (ESI): calc. for [(C16H19NO3)H] (M+H) 274.1443, measured 274.1446.
IR (ATR)ṽ (cm-1
): 2989, 2717, 1637, 1485, 1212, 1041, 908, 875, 652.
Rf (hexane/ethyl acetate = 70:30): 0.23.
(4-(Pent-2-en-1-yl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3ac).
The representative general procedure was followed using 1a (100 mg), 2c (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 101 mg and yield is
77%. Colorless liquid; eluent (30% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): E isomer: 6.66 (d, J = 8.0 Hz, 1H),6.63 (d, J = 8.0 Hz,
1H),5.93 (s, 2H), 5.38 – 5.32 (m, 2H), 3.55 (t, J = 8.0 Hz, 2H), 3.37 (d, J = 8.0 Hz, 2H), 3.14
(t, J = 8.0 Hz, 2H), 2.08 (p, J = 8.0 Hz, 2H), 1.89 (p, J = 8.0 Hz, 2H), 1.78 (p, J = 8.0 Hz,
2H), 0.93 (t, J = 8.0 Hz, 3H).Z isomer: 6.66 (d, J = 8.0 Hz, 1H),6.63 (d, J = 8.0 Hz, 1H),
5.93 (s, 2H), 5.48 – 5.43 (m, 2H), 3.55 (t, J = 8.0 Hz, 2H), 3.31 (d, J = 8.0 Hz, 2H), 3.14 (t, J
= 8.0 Hz, 2H), 2.08 (p, J = 8.0 Hz, 2H), 1.89 (p, J = 8.0 Hz, 2H), 1.78 (p, J = 8.0 Hz, 2H),
0.93 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): E isomer: 169.1, 147.3, 146.1, 133.4, 132.6, 131.7, 125.5,
119.9, 106.1, 100.9, 48.9, 45.4, 25.9, 24.8, 24.6, 20.5, 14.1. Z isomer: 170.7, 147.3, 146.1,
130.5, 125.4, 125.3, 119.7, 119.6, 106.1, 100.9, 48.9, 45.4, 39.0, 34.7, 29.8, 25.9, 25.4, 24.9,
24.8, 24.6, 20.5, 14.1, 13.5.
HRMS (ESI): calc. for [(C17H21NO3)H] (M+H) 288.1600, measured 288.1610.
IR (ATR)ṽ (cm-1
): 2948, 2811, 1616, 1435, 1212, 1021, 905, 875, 669.
13
Rf (hexane/ethyl acetate = 70:30): 0.23.
(4-(Hex-2-en-1-yl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3ad).
The representative general procedure was followed using 1a (100 mg), 2d (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 103 mg and yield is
76%. Colorless liquid; eluent (26% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): E isomer: 6.66 (d, J = 8.0 Hz, 1H), 6.62 (d, J = 8.0 Hz, 1H),
5.92 (s, 2H), 5.38 – 5.33 (m, 2H), 3.55 (t, J = 8.0 Hz, 2H), 3.36 (d, J = 4.0 Hz, 2H), 3.13 (t, J
= 8.0 Hz, 2H), 2.05 (q, J = 8.0 Hz, 2H), 1.89 (p, J = 8.0 Hz, 2H), 1.77 (p, J = 8.0 Hz, 2H),
5.38 – 5.33 (m, 2H), 0.87 (t, J = 8.0 Hz, 3H).
Z isomer: 6.66 (d, J = 8.0 Hz, 1H), 6.62 (d, J = 8.0 Hz, 1H), 5.92 (s, 2H), 5.47 – 5.41 (m,
2H), 3.55 (t, J = 8.0 Hz, 2H), 3.31 (d, J = 4.0 Hz, 2H), 3.13 (t, J = 8.0 Hz, 2H), 2.05 (q, J =
8.0 Hz, 2H), 1.89 (p, J = 8.0 Hz, 2H), 1.77 (p, J = 8.0 Hz, 2H), 5.38 – 5.33 (m, 2H), 0.81 (t, J
= 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): E isomer: 170.7, 147.2, 146.0, 131.7, 130.8, 126.2, 126.0,
119.7, 106.2, 100.9, 48.8, 45.4, 29.2, 25.8, 24.9, 24.5, 22.7, 13.7.
Z isomer: 169.1, 147.2, 146.0, 130.4, 126.5, 120.1, 119.9, 119.7, 106.2, 100.9, 48.8, 39.0,
34.7, 34.5, 29.9, 25.0, 22.4, 13.6.
HRMS (ESI): calc. for [(C18H23NO3)H] (M+H) 302.1756, measured 302.1762.
IR (ATR)ṽ (cm-1
): 2967, 2819, 1614, 1435, 1312, 1041, 908, 818, 695.
Rf (hexane/ethyl acetate = 70:30): 0.29.
14
(4-(Oct-2-en-1-yl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3ae).
The representative general procedure was followed using 1a (100 mg), 2e (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 102 mg and yield is
68%. Colorless liquid; eluent (28% ethylacetate in hexane).
1H NMR (CDCl3, 400 MHz): E isomer: 6.65 (d, J = 8.0 Hz, 1H), 6.61 (d, J = 8.0 Hz, 1H),
5.91 (s, 2H), 5.37 – 5.35 (m, 2H), 3.54 (t, J = 8.0 Hz, 2H), 3.35 (d, J = 4.0 Hz, 2H), 3.13 (t, J
= 8.0 Hz, 2H), 2.06 (q, J = 8.0 Hz, 2H), 1.88 (p, J = 8.0 Hz, 2H), 1.77 (p, J= 8.0 Hz, 2H),
1.36 – 1.16 (m, 6H), 0.84 (t, J = 8.0 Hz, 3H). Z isomer: 6.65 (d, J = 8.0 Hz, 1H), 6.61 (d, J
= 8.0 Hz, 1H), 5.91 (s, 2H), 5.43 – 5.40 (m, 1H), 3.54 (t, J = 8.0 Hz, 2H), 3.29 (d, J = 4.0 Hz,
2H), 3.13 (t, J = 8.0 Hz, 2H), 2.06 (q, J = 8.0 Hz, 2H), 1.88 (p, J = 8.0 Hz, 2H), 1.77 (p, J=
8.0 Hz, 2H), 1.36 – 1.16 (m, 6H), 0.84 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): E isomer: 169.1, 147.2, 146.1, 131.7, 131.1, 125.9, 119.9,
119.7, 106.1, 100.9, 48.8, 45.4, 31.4, 29.2, 27.1, 25.9, 24.9, 24.5, 22.5, 13.9. Z isomer:
169.1, 147.2, 146.1, 131.9, 131.1, 126.2, 119.9, 119.7, 106.1, 100.9, 48.8, 36.5, 34.7, 32.4,
31.3, 29.9, 29.6, 28.9, 22.4, 13.9.
HRMS (ESI): calc. for [(C20H27NO3)H] (M+H) 330.2069, measured 330.2077.
Rf (hexane/ethyl acetate = 70:30): 0.23.
(4-(3-Cyclohexylallyl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3af).
15
The representative general procedure was followed using 1a (100 mg), 2f (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 96 mg and yield is 62%.
Colorless liquid; eluent (30% ethyl acetate in hexanes).
1H NMR (CDCl3, 400 MHz): E isomer: δ 6.67 (d, J = 8.0 Hz, 1H), 6.64 (d, J = 8.0 Hz, 1H),
5.93 (s, 2H), 5.31 – 5.18 (m, 2H), 3.57 (t, J = 8.0 Hz, 2H), 3.38 (d, J = 8.0 Hz, 2H), 3.16 (t, J
= 8.0 Hz, 2H), 2.39 – 2.32 (m, 1H), 1.90 (p, J = 8.0 Hz, 2H), 1.79 (p, J = 8.0 Hz, 2H), 1.68 –
1.56 (m, 6H), 1.35 – 1.19 (m, 2H), 1.19 – 1.07 (m, 2H), 1.07 – 0.93 (m, 2H).
Z isomer: δ 6.67 (d, J = 8.0 Hz, 1H), 6.64 (d, J = 8.0 Hz, 1H), 5.93 (s, 2H), 5.41 – 5.38 (m,
2H), 3.57 (t, J = 8.0 Hz, 2H), 3.30 (d, J = 8.0 Hz, 2H), 3.16 (t, J = 8.0 Hz, 2H), 2.39 – 2.32
(m, 1H), 1.90 (p, J = 8.0 Hz, 2H), 1.79 (p, J = 8.0 Hz, 2H), 1.68 – 1.56 (m, 6H), 1.35 – 1.19
(m, 2H), 1.19 – 1.07 (m, 2H), 1.07 – 0.93 (m, 2H).
13C NMR (CDCl3, 100 MHz): E isomer: 169.1, 147.3, 146.1, 137.1, 131.7, 124.3, 120.2,
119.8, 106.2, 100.9, 48.9, 45.5, 36.2, 33.1, 26.0, 25.9, 25.8, 25.1, 24.6. Z isomer: 169.1,
137.9, 137.8, 137.1, 130.5, 124.1, 123.9, 119.8, 106.2, 100.9, 48.9, 45.5, 40.5, 39.1, 34.8,
32.9, 30.2, 29.6, 26.1.
HRMS (ESI): calc. for [(C21H27NO3)H] (M+H) 342.2069, measured 342.2073.
Rf (hexane/ethyl acetate = 98:2): 0.63.
(4-(3-Phenylallyl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (3ag).
The representative general procedure was followed using 1a (100 mg), 2g (2.5 equiv) and the
reaction was done at rt for 16 h. The desired product was isolated in 113 mg and yield is
74%. Colorless liquid; eluent (27% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): E isomer: δ 7.35 – 7.17 (m, 6H), 6.67 (s, 2H), 6.43 (dt, J =
12.0, 4.0 Hz, 1H), 5.94 (s, 2H), 5.74 (dt, J = 12.0, 8.0 Hz, 1H), 3.68 (dd, J = 8.0, 4.0 Hz, 2H),
3.29 (t, J = 8.0 Hz, 2H), 3.05 (t, J = 8.0 Hz, 2H), 1.74 – 1.62 (m, 4H).
16
Z isomer: δ 7.35 – 7.17 (m, 6H), 6.67 (s, 2H), 6.43 (dt, J = 12.0, 4.0 Hz, 1H), 5.94 (s, 2H),
5.74 (dt, J = 12.0, 8.0 Hz, 1H), 3.56 (dd, J = 8.0, 4.0 Hz, 2H), 3.52 (t, J = 8.0 Hz, 2H), 3.11 (t,
J = 8.0 Hz, 2H), 1.74 – 1.62 (m, 4H).
13C NMR (CDCl3, 100 MHz): E isomer: 168.7, 147.3, 145.9, 136.8, 131.9, 129.4, 128.7,
128.1, 126.7, 119.6, 119.1, 106.6, 101.0, 48.6, 45.5, 26.5, 25.7, 24.3.
Z isomer: 168.9, 146.1, 137.1, 131.7, 131.1, 128.4, 127.1, 126.6, 125.9, 119.9, 118.8,
106.2, 101.0, 49.0, 45.1, 29.9, 29.6, 25.6.
HRMS (ESI): calc. for [(C21H21NO3)H] (M+H) 336.1600, measured 336.1607.
Rf (hexane/ethyl acetate = 70:30): 0.27.
(E)-(4-(Prop-1-en-1-yl)benzo[d][1,3]dioxol-5-yl)(pyrrolidin-1-yl)methanone (4aa).
The representative general procedure was followed using 1a (100 mg), 2a (1.2 equiv) and the
reaction was done at 100οC for12 h. The desired product was isolated in 89 mg and yield is
76%. Colorless solid; eluent (30% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): δ 6.71 (d, J = 8.0 Hz, 1H), 6.65 (d, J = 8.0 Hz, 1H), 6.55 (dq, J
= 16.0, 8.0 Hz, 1H), 6.22(dq, J = 16.0, 4.0 Hz, 1H), 5.98 (s, 2H), 3.61 (t, J = 8.0 Hz, 2H),
3.12 (t, J = 8.0 Hz, 2H), 1.91 (p, J = 8.0 Hz, 2H), 1.84 (dd, J = 8.0, 4.0 Hz, 3H), 1.84 – 1.78
(m, 2H).
13C NMR (CDCl3, 100 MHz): 169.1, 147.6, 144.8, 132.6, 130.7, 122.9, 119.9, 117.5, 106.6,
100.9, 48.4, 45.5, 25.9, 24.6, 19.4.
HRMS (ESI): calc. for [(C15H17NO3)H] (M+H) 260.1287, measured 260.1289.
IR (ATR)ṽ (cm-1
): 2881, 2797, 1647, 1435, 1312, 1041, 918, 874, 680.
Rf (hexane/ethyl acetate = 70:30): 0.22.
(E)-(4-Methoxy-2-(prop-1-en-1-yl)phenyl)(pyrrolidin-1-yl)methanone (4ba).
17
The representative general procedure was followed using 1b (100 mg), 2a (1.2 equiv) and the
reaction was done at 100οC for12 h. The desired product was isolated in 88 mg and yield is
74%. Colorless solid; eluent (28% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.13 (d, J = 8.0 Hz, 1H), 6.96 (d, J = 4.0 Hz, 1H), 6.74 (dd, J
= 8.0, 4.0 Hz, 1H), 6.39 (d, J = 16.0 Hz, 1H), 6.25 – 6.16 (m, 1H), 3.79 (s, 3H), 3.62 (t, J =
8.0 Hz, 2H), 3.09 (t, J = 8.0 Hz, 2H), 1.91 (p, J = 8.0 Hz, 2H), 1.83 (dd, J = 8.0, 4.0 Hz, 2H),
1.82 – 1.77 (m, 2H).
13C NMR (CDCl3, 100 MHz): 169.7, 159.8, 135.9, 129.1, 128.5, 127.8, 127.6, 112.6, 110.4,
55.2, 48.3, 45.5, 25.9, 24.6, 18.7.
HRMS (ESI): calc. for [(C15H19NO2)H] (M+H) 246.1494, measured 246.1502.
IR (ATR)ṽ (cm-1
): 2931, 2817, 1727, 1637, 1435, 1312, 1041, 908, 875, 661.
Rf (hexane/ethyl acetate = 70:30): 0.32.
(E)-(4-Methyl-2-(prop-1-en-1-yl)phenyl)(pyrrolidin-1-yl)methanone (4ca).
The representative general procedure was followed using 1c (100 mg), 2a (1.2 equiv) and the
reaction was done at 100οC for12 h. The desired product was isolated in 98 mg and yield is
81%. Colorless solid; eluent (28% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.25 (s, 1H), 7.06 (d, J = 8.0 Hz, 1H), 6.99 (d, J = 8.0 Hz,
1H), 6.36 (d, J = 16.0 Hz, 1H), 6.23- 6.15 (m, 1H), 3.61 (t, J = 8.0 Hz, 2H), 3.06 (t, J = 8.0
Hz, 2H), 2.29 (s, 3H), 1.90 (p, J = 8.0 Hz, 2H), 1.81 (dd, J = 8.0, 4.0 Hz, 3H), 1.81 – 1.75(m,
2 H).
18
13C NMR (CDCl3, 100 MHz): 169.9, 138.5, 133.9, 133.3, 127.9, 127.6, 127.5, 126.0, 125.9,
48.2, 45.4, 25.8, 24.5, 21.3, 18.7.
HRMS (ESI): calc. for [(C15H19NO)H] (M+H) 230.1545, measured 230.1553.
IR (ATR)ṽ (cm-1
): 2942, 2617, 1647, 1415, 1317, 1047, 918, 875, 598.
Rf (hexane/ethyl acetate = 70:30): 0.29.
(E)-(2-(Prop-1-en-1-yl)phenyl)(pyrrolidin-1-yl)methanone (4da).
The representative general procedure was followed using 1d (100 mg), 2a (1.2 equiv) and the
reaction was done at 100 οC for 12 h. The desired product was isolated in 92 mg and yield is
75%. Colorless solid; eluent (27% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.40 (d, J = 8.0Hz,1H),7.24 -7.18 (m, 1H), 7.12 (t, J =
4.0Hz,2H),6.33 (d, J = 16.0Hz,1H),6.20 -6.13(m, 1H), 3.57 (t, J = 8.0Hz,2 H), 3.00 (t, J =
8.0Hz,2 H), 1.85 (p, J = 4.0Hz,2 H), 1.77(dt, J = 8.0, 4.0Hz,3 H), 1.76 – 1.72 (m, 2 H).
13C NMR (CDCl3, 100 MHz): 169.5, 135.8, 133.8, 128.7, 128.2, 127.4, 126.7, 125.8, 125.2,
48.0, 45.2, 25.7, 24.4, 18.6.
HRMS (ESI): calc. for [(C14H17NO)H] (M+H) 216.1388, measured 216.1395.
Rf (hexane/ethyl acetate = 70:30): 0.33.
(E)-(4-Chloro-2-(prop-1-en-1-yl)phenyl)(pyrrolidin-1-yl)methanone (4fa).
19
The representative general procedure was followed using 1f (100 mg), 2a (1.2 equiv) and the
reaction was done at 120οC for12 h. The desired product was isolated in 86 mg and yield is
73%. Colorless solid; eluent (28% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.45 (d, J = 4.0 Hz, 1H), 7.17 (dd, J = 8.0, 4.0 Hz, 1H), 7.13
(d, J = 8.0 Hz, 1H), 6.35 (d, J = 16.0 Hz, 1H), 6.29 – 6.21 (m, 1H), 3.63 (t, J = 8.0 Hz, 2H),
3.07 (t, J = 8.0 Hz, 2H), 1.93 (p, J = 6.5 Hz, 2H), 1.85 (dd, J = 8.0, 2.0 Hz, 3H), 1.84 – 1.78
(m, 2H).
13C NMR (CDCl3, 100 MHz): 168.7, 136.1, 134.8, 134.5, 129.3, 127.6, 126.9, 126.6, 125.5,
48.2, 45.5, 25.9, 24.6, 18.7.
HRMS (ESI): calc. for [(C14H16ClNO)H] (M+H) 250.0999, measured 250.1003.
Rf (hexane/ethyl acetate = 70:30): 0.29.
(E)-(4-Fluoro-2-(Prop-1-en-1-yl)phenyl)(pyrrolidin-1-yl)methanone (4ga).
The representative general procedure was followed using 1g (100 mg), 2a (1.2 equiv) and the
reaction was done at 120οC for12 h. The desired product was isolated in 75 mg and yield is
62%. Colorless solid; eluent (28% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.17 (d, J = 8.0Hz,1H),7.13 (dd, J = 8.0, 4.0Hz,1H),6.88(dt, J
= 8.0, 4.0 Hz,1H),6.35 (d, J = 16.0Hz,1H),6.27 -6.18(m, 1H), 3.61 (t, J = 8.0Hz,2H), 3.06 (t,
J = 8.0Hz,2H), 1.91 (p, J = 4.0Hz,2H), 1.83(dd, J = 8.0, 4.0Hz,3H), 1.81 – 1.77(m, 2H).
13C NMR (CDCl3, 100 MHz): 168.9, 164.1 and 161.6 (F-coupling), 136.8 and 136.7 (F-
coupling), 132.1, 129.8, 128.1 and 127.9 (F-coupling), 126.7, 114.0 and 113.8 (F-coupling),
111.9 and 111.7 (F-coupling), 48.3, 45.5, 25.9, 24.5, 18.7.
HRMS (ESI): calc. for [(C14H16FNO)H] (M+H) 234.1294, measured 234.1299.
Rf (hexane/ethyl acetate = 98:2): 0.63.
20
(E)-N,4-Dimethyl-2-(prop-1-en-1-yl)benzamide (4ja).
The representative general procedure was followed using 1j (100 mg), 2a (2.0 equiv) and the
reaction was done at 100οC for 16 h. The desired product was isolated in 79 mg and yield is
63%. White Colour solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.29 (d, J = 4.0Hz, 1H), 7.25 (d, J = 4.0 Hz, 1H), 7.00 (d, J =
8.0Hz, 1H), 6.67 (dd, J = 16.0, 4.0 Hz, 1H), 6.20-6.11 (m, 1H), 5.81 (s, 1H), 2.95 (d, J = 4.0
Hz,3 H), 2.32 (s, 3 H), 1.86 (dd, J = 8.0, 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 170.3, 139.9, 135.9, 132.0, 128.6, 128.4, 127.5, 127.4, 126.9,
26.7, 21.3, 18.7.
HRMS (ESI): calc. for [(C12H15NO)H] (M+H) 190.1232, measured 190.1236.
IR (ATR)ṽ (cm-1
): 3289, 2922, 1630, 1536, 1403, 1157, 1041, 999.
Rf (hexane/ethyl acetate = 70:30): 0.27.
(E)-N-Methyl-2-(prop-1-en-1-yl)benzamide(4ka).
The representative general procedure was followed using 1k (100 mg), 2a (2.0 equiv) and the
reaction was done at 100οC for 16 h. The desired product was isolated in 84 mg and yield is
65%. White Colour solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.44 (d, J = 4.0Hz, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.29 (d, J =
8.0 Hz, 1H),7.16 (t, J = 8.0 Hz, 1H), 6.65 (d, J = 12.0Hz, 1H), 6.20-6.11 (m, 1H), 5.92 (s, 1
H), 2.93(d, J = 4.0 Hz, 3 H), 1.85 (dd, J = 8.0, 4.0Hz, 3 H).
21
13C NMR (CDCl3, 100 MHz): 170.3, 135.8, 134.8, 129.8, 128.6, 128.3, 127.3, 126.6, 126.1,
26.6, 18.6.
HRMS (ESI): calc. for [(C11H13NO)H] (M+H) 176.1075, measured 176.1073.
IR (ATR)ṽ (cm-1
): 3294, 2935, 1635, 1546, 1444, 1319, 1005, 954, 687.
Rf (hexane/ethyl acetate = 70:30): 0.21.
(E)-4-Bromo-N-methyl-2-(prop-1-en-1-yl)benzamide (4la).
The representative general procedure was followed using 1l (100 mg), 2a (2.0 equiv) and the
reaction was done at 120οC for 20 h. The desired product was isolated in 66 mg and yield is
56%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.59 (d, J = 4.0Hz, 1 H), 7.31 (dd, J = 8.0, 4.0 Hz, 1 H), 7.24
(d, J = 8.0 Hz, 1 H), 6.60 (dd, J = 16.0, 4.0 Hz, 1 H), 6.23-6.14 (m, 1 H), 5.83 (s, 1 H),
2.96(d, J = 4.0 Hz,3 H), 1.87 (dd, J = 8.0, 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 169.4, 137.9, 133.5, 130.3, 129.6, 129.2, 128.9, 127.2, 124.3,
26.7, 18.7.
HRMS (ESI): calc. for [(C11H12BrNO)H] (M+H) 254.0181, measured 254.0188.
IR (ATR)ṽ (cm-1
): 3282, 2945, 2817, 1635, 1547, 1441, 1312, 1041, 935, 875, 661.
Rf (hexane/ethyl acetate = 70:30): 0.29.
(E)-4-Chloro-N-methyl-2-(prop-1-en-1-yl)benzamide (4ma).
22
The representative general procedure was followed using 1m (100 mg), 2a (2.0 equiv) and
the reaction was done at 120 οC for 20 h. The desired product was isolated in 66 mg and yield
is 54%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.42 (d, J = 4.0Hz, 1 H), 7.29 (dd, J = 8.0, 4.0 Hz, 1 H), 7.14
(dt, J = 8.0, 4.0 Hz, 1 H), 6.60 (d, J = 16.0Hz, 1 H), 6.23-6.14 (m, 1 H), 5.89 (s, 1 H), 2.94
(dd, J =8.0, 4.0 Hz,3 H), 1.87 (d, J = 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 169.4, 137.8, 135.9, 133.1, 130.2, 128.8, 127.3, 126.7, 126.2,
26.7, 18.7.
HRMS (ESI): calc. for [(C11H12ClNO)H] (M+H) 210.0686, measured 210.0691.
IR (ATR)ṽ (cm-1
): 3078, 2931, 1634, 1589, 1463, 1259, 1041, 874, 747, 668.
Rf(hexane/ethyl acetate = 70:30): 0.30.
(E)-4-Fluoro-N-methyl-2-(prop-1-en-1-yl)benzamide (4na).
The representative general procedure was followed using 1n (100 mg), 2a (2.0 equiv) and the
reaction was done at 120οC for 20 h. The desired product was isolated in 47 mg and yield is
42%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.38 (dd, J = 8.0, 4.0 Hz, 1H), 7.14 (dd, J = 8.0, 4.0 Hz, 1H),
6.88 (td, J = 8.0, 4.0 Hz, 1H), 6.67 (dt, J = 16.0, 4.0 Hz, 1H), 6.20 (dq, J = 12.0, 4.0 Hz, 1H),
5.78(s, 1H), 2.97 (d, J = 4.0Hz, 3H), 1.88(dd, J = 8.0, 4.0 Hz,3H).
13C NMR (CDCl3, 100 MHz): 169.5, 164.8, 162.3, 138.7 and 138.6 (F-coupling), 130.9,
130.1, 129.6 and 129.5 (F-coupling), 127.5, 113.8 and 113.6 (F-coupling), 112.8 and 112.6
(F-coupling), 26.8, 18.7.
HRMS (ESI): calc. for [(C11H12FNO)H] (M+H) 194.0981, measured 194.0988.
Rf(hexane/ethyl acetate = 70:30): 0.31.
23
(E)-N,2-Dimethyl-6-(prop-1-en-1-yl)benzamide (4oa).
The representative general procedure was followed using 1o (100 mg), 2a (2.0 equiv) and the
reaction was done at 100οC for 16 h. The desired product was isolated in 104 mg and yield is
83%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.27 (d, J = 8.0Hz, 1 H), 7.14 (t, J = 8.0 Hz, 1 H), 6.99 (d, J =
4.0 Hz, 1 H), 6.36 (d, J = 16.0,Hz, 1 H), 6.19-6.13 (m, 1 H), 5.75 (s, 1 H), 2.95 (d, J = 8.0
Hz,3 H), 2.25 (s, 3 H), 1.82 (dd, J = 8.0, 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 170.8, 135.7, 134.7, 134.5, 128.7, 128.4, 128.2, 127.8, 122.5,
26.4, 19.1, 18.7.
HRMS (ESI): calc. for [(C12H15NO)H] (M+H) 190.1232, measured 190.1236.
Rf (hexane/ethyl acetate = 70:30): 0.28.
(E)-5-Chloro-N-methyl-2-(prop-1-en-1-yl)benzamide (4pa).
The representative general procedure was followed using 1m (100 mg), 2a (2.0 equiv) and
the reaction was done at 120οC for 20 h. The desired product was isolated in 64 mg and yield
is 51%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.39 (d, J = 8.0Hz, 1 H), 7.35 (d, J = 4.0 Hz, 1 H), 7.27 (dd, J
= 8.0, 4.0 Hz, 1 H), 6.59 (d, J = 16.0Hz, 1 H), 6.21-6.12 (m, 1 H), 5.86 (s, 1 H), 2.96 (d, J =
8.0 Hz, 3 H), 1.86 (dd, J = 8.0, 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 168.9, 136.0, 134.4, 132.4, 130.0, 129.5, 127.6, 127.4, 127.3,
26.7, 18.7.
24
HRMS (ESI): calc. for [(C11H12ClNO)H] (M+H) 210.0686, measured 210.0685.
Rf (hexane/ethyl acetate = 70:30): 0.21.
(E)-N-Methyl-3-(prop-1-en-1-yl)-2-naphthamide (4qa).
The representative general procedure was followed using 1i (100 mg), 2a (2.0 equiv) and the
reaction was done at 100οC for 16 h. The desired product was isolated in 93 mg and yield is
77%. Colorless solid; eluent (0.3% methanol in DCM).
1H NMR (CDCl3, 400 MHz): 7.88 (s, 1 H), 7.86 (s, 1 H), 7.76 (t, J = 8.0 Hz,2 H), 7.47 (t, J
= 8.0 Hz, 1 H), 7.41 (t, J = 8.0 Hz, 1 H), 6.76 (d, J = 16.0Hz, 1 H), 6.31-6.22 (m, 1 H), 5.99
(s, 1 H), 3.01 (d, J = 8.0 Hz,3 H), 1.91 (dd, J = 8.0, 4.0Hz, 3 H).
13C NMR (CDCl3, 100 MHz): 170.3, 133.9, 133.5, 133.5, 131.6, 128.8, 128.6, 127.9, 127.6,
127.3, 127.2, 126.1, 125.2, 26.8, 18.8.
HRMS (ESI): calc. for [(C15H15NO)H] (M+H) 226.1232, measured 226.1236.
Rf (hexane/ethyl acetate = 98:2): 0.63.
8-Methyl-8,9-dihydro-6H-[1,3]dioxolo[4,5-f]isochromen-6-one (5a).
The representative general procedure was followed using 3aa (50 mg) and the reaction was
done at 110οC for 12 h. The desired product was isolated in 25 mg and yield is 64%.
Colorless solid; eluent (11% ethylacetate in hexanes).
25
1H NMR (CDCl3, 400 MHz): 7.45 (d, J = 8.0 Hz, 1H), 6.95 (d, J = 8.0 Hz, 1H), 6.12 (d, J=
4.0 Hz, 1H), 6.09 (d, J = 4.0 Hz, 1H), 5.42 (dd, J = 8.0, 4.0 Hz, 1H), 2.16 – 2.08 (m, 1H),
1.88 – 1.78 (m, 1H), 0.99 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 165.1, 151.6, 143.8, 126.3, 119.8, 118.8, 107.6, 102.3, 74.6,
28.6, 20.9.
HRMS (ESI): calc. for [(C11H10O4)H] (M+H) 207.0657, measured 207.0659.
IR (ATR)ṽ (cm-1
): 2927, 2854, 1707, 1589, 1232, 1116, 1041, 908, 845, 664.
Rf (hexane/ethyl acetate = 80:20): 0.38.
6-Methoxy-3-methylisochroman-1-one (5b).
The representative general procedure was followed using 3ba (50 mg) and the reaction was
done at 110οC for 12 h. The desired product was isolated in 27 mg and yield is 61%.
Colorless solid; eluent (10% ethyl acetate in hexanes).
1H NMR (CDCl3, 400 MHz): 8.02 (d, J = 8.0 Hz, 1H), 6.86 (dd, J = 8.0, 4.0 Hz, 1H),6.67
(d, J = 4.0 Hz, 1H), 4.67 – 4.59 (m, 1H), 3.84 (s, 3H), 2.92 (dd, J = 16.0, 8.0 Hz, 1H), 2.84
(dd, J = 16.0, 4.0 Hz, 1H),1.48 (d, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 165.5, 163.7, 141.4, 132.6, 117.5, 113.4, 112.1, 74.7, 55.5,
35.2, 20.9.
HRMS (ESI): calc. for [(C11H12O3)H] (M+H) 193.0865, measured 193.0874.
IR (ATR)ṽ (cm-1
): 2980, 2935, 1713, 1607, 1458, 1117, 1041, 908, 741, 691.
Rf (hexane/ethyl acetate = 80:20): 0.48.
3,6-Dimethylisochroman-1-one (5c).
26
The representative general procedure was followed using 3ca (50 mg) and the reaction was
done at 110οC for12 h. The desired product was isolated in 24 mg and yield is 62%. Colorless
solid; eluent (10% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.95 (d, J = 8.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, 1H), 7.01 (s,
1H), 4.67 -4.58 (m, 1 H), 2.90 (dd, J = 16.0, 8.0 Hz, 1H), 2.83 (dd, J = 16.0, 8.0 Hz, 1H),
2.37 (s, 3H), 1.48 (d, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 165.8, 144.6, 139.1, 130.3, 128.5, 127.8, 122.3, 74.9, 34.9,
21.7, 20.9.
HRMS (ESI): calc. for [(C11H12O2)H] (M+H) 177.0916, measured 177.0923.
Rf (hexane/ethyl acetate = 80:20): 0.43.
3-Methylisochroman-1-one (5d).
The representative general procedure was followed using 3da (50 mg) and the reaction was
done at 110οCfor 12 h. The desired product was isolated in 22 mg and yield is 58%. Colorless
solid; eluent (10% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 8.07 (d, J = 8.0 Hz, 1H), 7.51 (td, J = 8.0, 4.0 Hz, 1H), 7.36
(t, J = 8.0 Hz, 1H), 7.21 (d, J = 8.0 Hz, 1H), 4.69 -4.64(m, 1 H), 2.96 (dd, J = 16.0, 8.0 Hz,
1H), 2.90 (dd, J = 16.0, 4.0 Hz, 1H),1.50 (d, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 165.6, 139.1, 133.6, 130.2, 127.6, 127.2, 124.9, 75.1, 34.9,
20.9.
HRMS (ESI): calc. for [(C10H10O2)H] (M+H) 163.0759, measured 163.0770.
Rf (hexane/ethyl acetate = 80:20): 0.43.
27
6-Chloro-3-methylisochroman-1-one (5ea).
The representative general procedure was followed using 3fa (50 mg) and the reaction was
done at 110οC for 12 h. The desired product was isolated in 20 mg and yield is 51%.
Colorless solid; eluent (10% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.99 (d, J = 8.0 Hz, 1H), 7.33 (dd, J = 8.0, 4.0 Hz, 1H), 7.22
(d, J = 4.0 Hz, 1H), 4.69 -4.61 (m, 1 H), 2.94 (dd, J = 16.0, 8.0 Hz, 1H), 2.87 (dd, J = 16.0,
4.0 Hz, 1H),), 1.49 (d, J = 6.3 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 164.7, 140.7, 139.9, 131.8, 128.1, 127.4, 123.4, 74.9, 34.6,
20.8.
Rf (hexane/ethyl acetate = 98:2): 0.63.
8-Ethyl-[1,3]dioxolo[4,5-e]isobenzofuran-6(8H)-one (6a).
The representative general procedure was followed using 4aa (50 mg) and the reaction was
done at 120 οC for 12 h. The desired product was isolated in 25 mg and yield is 61%.
Colorless solid; eluent (10% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.45 (d, J = 8.0 Hz, 1H), 6.95 (d, J = 8.0 Hz, 1H), 6.12 (d, J =
4.0 Hz, 1H), 6.09 (d, J = 4.0 Hz, 1H), 5.42 (dd, J = 8.0, 4.0 Hz, 1H), 2.16 -2.08(m, 1 H), 1.83
(dq, J = 12.0, 4.0 Hz, 1H), 0.99 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 169.7, 152.4, 141.1, 129.2, 121.3, 120.8, 109.9, 102.6, 79.6,
26.7, 8.8.
HRMS (ESI): calc. for [(C11H10O4)H] (M+H) 207.0657, measured 207.0666.
28
IR (ATR)ṽ (cm-1
): 2931, 2817, 1727, 1637, 1435, 1312, 1041, 908, 875, 661.
Rf (hexane/ethyl acetate = 80:20): 0.33.
3-Ethyl-5-methoxyisobenzofuran-1(3H)-one (6b).
The representative general procedure was followed using 4ba (50 mg) and the reaction was
done at 120 οC for 12 h. The desired product was isolated in 22 mg and yield is 56%.
Colorless solid; eluent (12% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 7.78 (d, J = 8.0 Hz, 1H), 7.00 (dd, J = 8.0, 4.0 Hz, 1H), 6.82
(d, J = 8.0 Hz, 1H), 5.35 (dd, J = 8.0, 4.0 Hz, 1H), 3.88 (s, 3H), 2.15 – 2.04 (m, 1H),1.84 –
1.73 (m, 1H), 0.98 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 170.4, 164.6, 152.5, 127.2, 118.7, 116.1, 105.8, 81.5, 55.8,
27.6, 8.7.
HRMS (ESI): calc. for [(C11H12O3)H] (M+H) 193.0865, measured 193.0874.
IR (ATR)ṽ (cm-1
): 2972, 2933, 1702, 1604, 1495, 1255, 1083, 1019, 689.
Rf (hexane/ethyl acetate = 80:20): 0.31.
3-Ethyl-5-methylisobenzofuran-1(3H)-one (6ca).
The representative general procedure was followed using 4ca (50 mg) and the reaction was
done at 120 οC for 12 h. The desired product was isolated in 19 mg and yield is 51%.
Colorless solid; eluent (12% ethylacetate in hexanes).
29
1H NMR (CDCl3, 400 MHz): 7.74 (d, J = 8.0 Hz, 1H), 7.32 – 7.27 (m, 1H), 7.21 – 7.17 (m,
1H), 5.36 (dd, J = 8.0, 4.0 Hz, 1H), 2.46 (s, 3H), 2.13 – 2.02 (m, 1H), 1.81 – 1.74 (m, 1H),
0.96 (t, J = 8.0 Hz, 3H).
13C NMR (CDCl3, 100 MHz): 170.7, 150.3, 145.1, 130.2, 125.4, 123.7, 122.0, 82.0, 27.7,
22.1, 8.8.
HRMS (ESI): calc. for [(C11H12O2)H] (M+H) 177.0916, measured 177.0923.
Rf (hexane/ethyl acetate = 80:20): 0.30.
(6-Methyl-1-oxo-1,2,3,4-tetrahydroisoquinolin-3-yl)methyl acetate (11a).
The representative general procedure was followed using 10a (100 mg), 2a (2.5 equiv) and
the reaction was done at rt for 36 h. The desired product was isolated in 58 mg and yield is
41%. Colorless solid; eluent (32% ethylacetate in hexanes).
1H NMR (DMSO d6, 400 MHz): 7.96 (s, 1H), 7.72 (d, J = 8.0 Hz, 1H), 7.15 (d, J = 8.0 Hz,
1H), 7.10 (s, 1H), 4.08 (dd, J= 12.0, 4.0 Hz, 1H), 3.92 (dd, J= 12.0, 4.0 Hz, 1H), 3.82 – 3.78
(m, 1H), 3.02 (dd, J = 16.0, 4.0 Hz, 1H), 2.81 (dd, J = 16.0, 8.0 Hz, 1H), 2.33 (s, 3H), 1.97 (s,
3H).
13C NMR (DMSO d6, 100 MHz): 170.3, 164.3, 142.0, 137.2, 128.3, 127.5, 127.0, 126.1,
65.1, 48.7, 29.5, 21.1, 20.6.
HRMS (ESI): calc. for [(C13H15NO3)H] (M+H) 234.1130, measured 234.1141.
IR (ATR)ṽ (cm-1
): 3300 (broad), 2926, 2315, 1649, 1615, 1454, 1337, 1080, 657.
Rf (hexane/ethyl acetate = 60:40): 0.23.
(1-Oxo-1,2,3,4-tetrahydroisoquinolin-3-yl)methyl acetate (11b).
30
The representative general procedure was followed using 10b (100 mg), 2a (2.5 equiv) and
the reaction was done at rt for 36 h. The desired product was isolated in 55 mg and yield is
38%. Colorless solid; eluent (32% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 8.04 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 8.0 Hz, 1H), 7.34 (t, J =
8.0 Hz, 1H), 7.19 (d, J = 8.0 Hz, 1H), 6.42 (s, 1H), 4.24 (dd, J = 12.0, 4.0 Hz, 1H), 4.05 (dd,
J = 12.0, 8.0 Hz, 1H), 4.02 – 3.91 (m, 1H), 3.02 (dd, J = 16.0, 4.0 Hz, 1H), 2.89 (dd, J = 16.0,
8.0 Hz, 1H), 2.06 (s, 3H).
IR (ATR)ṽ (cm-1
): 2931, 2817, 1727, 1637, 1435, 1312, 1041, 908, 875, 661.
Rf (hexane/ethyl acetate = 60:40): 0.24.
(1-Oxo-1,2,3,4-tetrahydrobenzo[g]isoquinolin-3-yl)methyl acetate (11c).
The representative general procedure was followed using 10c (100 mg), 2a (2.5 equiv) and
the reaction was done at rt for 36 h. The desired product was isolated in 63 mg and yield is
47%. Colorless solid; eluent (32% ethylacetate in hexanes).
1H NMR (CDCl3, 400 MHz): 8.62 (s, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz,
1H), 7.63 (s, 1H), 7.53 (d, J = 8.20 Hz, 1H), 7.48 (t, J = 8.0 Hz, 1H), 6.47 (s, 1H), 4.27 (dd, J
= 12.0, 4.0 Hz, 1H), 4.07 (dd, J = 12.0, 4.0 Hz, 1H), 4.02 – 3.98 (m, 1H), 3.20 (dd, J = 16.0,
4.0 Hz, 1H), 3.04 (dd, J = 16.0, 4.0 Hz, 1H), 2.06 (s, 3H).
13C NMR (CDCl3, 100 MHz): 170.7, 166.3, 135.4, 132.3, 132.1, 129.6, 129.4, 128.7, 128.5,
127.1, 126.3, 126.2, 65.9, 50.2, 30.6, 20.7.
HRMS (ESI): calc. for [(C16H16NO3)H] (M+H) 270.1130, measured 270.1140.
IR (ATR)ṽ (cm-1
): 3267 (broad), 1734, 1727, 1656, 1413, 1229, 1042, 730.
Rf (hexane/ethyl acetate = 60:40): 0.28.
31
Deuterium Studies
To know the feasibility of C-H bond activation of N-methyl benzamide and N,N-disubstituted
benzamide at room temperature, the following deuterium labelling experiment was done.
Treatment of 1kwith CD3COOD in the presence of [{RuCl2(p-cymene)}2] (5.0 mol %) and
AgSbF6 (20 mol %) in 1,2-dichloroethane at room temperature for 4 h gave product 1k‘ in
96% yield with 72% and 73% of deuterium incorporation at the both ortho carbons. But, N,N-
disubstituted benzamide 1d under similar reaction conditions provided product 1d‘ in 97%
yield with 12% and 16% of deuterium incorporation at the both ortho carbons. The maximum
deuterium incorporation at the both ortho carbons of product 1d‘ in 78% and 79% were
observed at room temperature for 28 h. Based on these dueterium studies, we concluded that
the C-H bond of N-methyl benzamides can be activated at room temperature within 4 h. But,
the allylation step needs a longer reaction time or the higher reaction temperature. In the case
of weak directing group such as N,N-disubstituted benzamide, the C-H bond activation can
also be done at room temperature, but the process is slow and needs a longer reaction time. In
addition when N,N-disubstituted benzamide1b was treated with allyl acetate (2a) in the
presence of [{RuCl2(p-cymene)}2] (5.0 mol %), AgSbF6 (20 mol %) and CD3COOD (2.0
equiv)in 1,2-dichloroethane (DCE) at room temperature for 36 h, ortho allylated benzamide
3ba was observed in 69% yield along with 33% deuterium incorporation at the ortho carbon.
This results clearly indicates that the ortho C-H bond cleavage of aromatic amide in
intermediate 8 is a reversible process.
32
1H NMR Spectra of Compound 1k’.
33
1H NMR Spectra of Compound 1b’
34
1H and
13C NMR Spectra of Compound 3ba’.
Mechanistic Studies for Double Bond Isomerization Reaction.
When ortho allylated benzamide 3ba was treated with CD3COOD (2.0 equiv) in the presence
of [{RuCl2(p-cymene)}2] (5.0 mol %), AgSbF6 (20 mol %) in 1,2-dichloroethane (DCE) at
100°C for 12 h, ortho vinylated benzamide 4ba was observed in 92% yield along with 96%
deuterium incorporation at the CH3 group attached with the vinyl carbon and 31% deuterium
incorporation was observed at the α position of the vinylic carbon.
35
1H and
13C NMR Spectra of Compound 3ba’.
Mechanistic Studies for Double Bond Isomerization Reaction.
The reaction temperature is crucial for the isomerization reaction so the temperature effect for
the conversion of 3ad to 4ad was studied completely. The reaction was carried out at
different temperature such as 50 C, 60 C, 70 C, 80 C, 90 C and 100 C at standard
reaction condition. Benzamide 1d was treated with allyl acetate (2a) in the presence of
[{RuCl2(p-cymene)}2] (5.0 mol %) and AgSbF6 (20 mol %) in 1,2-dichloroethane (DCE) at
mentioned temperature for 36 h, Then, the reaction mixture was diluted with CH2Cl2, filtered
through Celite and the filtrate was concentrated. The crude residue was purified by column
chromatography to find out the yield. Later, 1H NMR analysis was done and the percentage
of the product 3da and 4da was determined by using 1H NMR integration method. The
characteristic proton for the both of the compounds 3da and 4da was analyzed in the crude
1H NMR data and the ratio of the products were calculated based on the integration. The
product yields are isolated yields.
36
Ha, Hb 5.09 – 5.01 (m, 2H); Hc 5.94 -5.86 (m, 1H); Hd 6.20 -6.13 (m, 1H); He 6.33 (d, J = 16.0 Hz, 1H).
Sl.no Reaction temperature
(C)
Ratio of the products in 1H
NMR
(3da : 4da)
Percentage of the products
(3da : 4da)
1 50 C 1 : 0 100 : 0
2 60 C 1 : 0.7 59 : 41
3 70 C 1 : 0.75 57 : 43
4 80 C 1 : 2 33 : 77
5 90 C 1 : 3.5 22 : 88
6 100 C 0 : 1 0 : 100
37
1H NMR Spectra of Crude reaction mixture 3d at 50 C.
1H NMR Spectra of Crude reaction mixture 3d at 60 C.
38
1H NMR Spectra of Crude reaction mixture 3d at 70 C.
1H NMR Spectra of Crude reaction mixture 3d at 80 C.
39
1H NMR Spectra of Crude reaction mixture 3d at 90C.
1H NMR Spectra of compound 4ad at 100C.
40
The energy of the molecules calculated by using DFT calculations.
Figure X. B3LYP/6-31G
(a) Optimized structure of compound 3da (b) Optimized structure of compound 4da
Molecule Energy
Compound 3da -673.69625741a.u -18332.2 eV
Compound 4da -673.70553985a.u -18332.4 eV
E = 0.2 eV = 19.29706 kJ/mol
Compound 4da is 19.2 kJ/mol is stabilized than Compound 3da.
Computational Details:
The ground state geometries were optimized without symmetry constraints using the B3LYP
functional2 in combination with the 6-31G(d) basis set
2 with the program package Gaussian
09 Revision C. 01.3 The optimized geometries were confirmed to be local minima by
performing vibrational frequency calculations and obtaining only positive (real) frequencies.
41
References:
1. (a) A. D. Becke, J. Chem. Phys., 1993, 98, 5648; (b) C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988,
37, 785; (c) P. J. Stephens, F. J. Devlin, C. F. Chabalowski and M. J. Frisch, J. Phys. Chem., 1994, 98,
11623.
2. (a) G. A. Petersson and M. A. Al-Laham, J. Chem. Phys., 1991, 94, 6081; (b) G. A. Petersson, A. Bennett, T.
G. Tensfeldt, M. A. Al-Laham, W. A. Shirley and J. Mantzaris, J. Chem. Phys., 1988, 89, 2193.
3. Gaussian 09, Revision C.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P.
Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada,M. Ehara, K. Toyota, R. Fukuda,
J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E.
Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R.
Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N.
Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.
E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma,
V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B.
Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2010.
42
1H and
13C NMR Spectra of Compound 3aa.
43
DEPT (135) NMR Spectrum of Compound 3aa.
44
1H and
13C NMR Spectra of Compound 3ba.
45
1H and
13C NMR Spectra of Compound 3ca.
46
DEPT (135) NMR Spectrum of Compound 3ca.
47
1H and
13C NMR Spectra of Compound 3da.
48
1H and
13C NMR Spectra of Compound 3ea.
49
1H and
13C NMR Spectra of Compound 3fa.
50
DEPT (135) NMR Spectrum of Compound 3fa.
51
1H and
13C NMR Spectra of Compound 3ga.
52
DEPT (135) NMR Spectrum of Compound 3ga.
53
1H and
13C NMR Spectra of Compound 3ha.
54
1H and
13C NMR Spectra of Compound 3ia.
55
1H and
13C NMR Spectra of Compound 3ab.
56
DEPT (135) NMR Spectrum of Compound 3ab.
57
1H and
13C NMR Spectra of Compound 3ac.
58
DEPT (135) NMR Spectrum of Compound 3ac.
59
1H and
13C NMR Spectra of Compound 3ad.
60
DEPT (135) NMR Spectrum of Compound 3ad.
61
1H and
13C NMR Spectra of Compound 3ae.
62
DEPT (135) NMR Spectrum of Compound 3ae.
63
1H and
13C NMR Spectra of Compound 3af.
64
DEPT (135) NMR Spectrum of Compound 3af.
65
1H and
13C NMR Spectra of Compound 3ag.
66
DEPT (135) NMR Spectrum of Compound 3ag.
67
1H and
13C NMR Spectra of Compound 4aa.
68
DEPT (135) NMR Spectrum of Compound 4aa.
69
1H and
13C NMR Spectra of Compound 4ba.
70
DEPT (135) NMR Spectrum of Compound 4ca.
71
1H and
13C NMR Spectra of Compound 4da.
72
DEPT (135) NMR Spectrum of Compound 4da.
73
1H and
13C NMR Spectra of Compound 4ea.
74
DEPT (135) NMR Spectrum of Compound 4ea.
75
1H and
13C NMR Spectra of Compound 4fa.
76
DEPT (135) NMR Spectrum of Compound 4fa.
77
1H and
13C NMR Spectra of Compound 4ga.
78
DEPT (135) NMR Spectrum of Compound 4ga.
79
1H and
13C NMR Spectra of Compound 4ja.
80
DEPT (135) NMR Spectrum of Compound 4ja.
81
1H and
13C NMR Spectra of Compound 4ka.
82
DEPT (135) NMR Spectrum of Compound 4ka.
83
1H and
13C NMR Spectra of Compound 4la.
84
DEPT (135) NMR Spectrum of Compound 4la.
85
1H and
13C NMR Spectra of Compound 4ma.
86
DEPT (135) NMR Spectrum of Compound 4ma.
87
1H and
13C NMR Spectra of Compound 4na.
88
DEPT (135) NMR Spectrum of Compound 4na.
89
1H and
13C NMR Spectra of Compound 4oa.
90
DEPT (135) NMR Spectrum of Compound 4oa.
91
1H and
13C NMR Spectra of Compound 4pa.
92
DEPT (135) NMR Spectrum of Compound 4pa.
93
1H and
13C NMR Spectra of Compound 4qa.
94
DEPT (135) NMR Spectrum of Compound 4qa.
95
1H and
13C NMR Spectra of Compound 5a.
96
DEPT (135) NMR Spectrum of Compound 5a.
97
1H and
13C NMR Spectra of Compound 5b.
98
DEPT (135) NMR Spectrum of Compound 5b.
99
1H and
13C NMR Spectra of Compound 5c.
100
DEPT (135) NMR Spectrum of Compound 5c.
101
1H and
13C NMR Spectra of Compound 5d.
102
DEPT (135) NMR Spectrum of Compound 5d.
103
1H and
13C NMR Spectra of Compound 5e.
104
DEPT (135) NMR Spectrum of Compound 5e.
105
1H and
13C NMR Spectra of Compound 6a.
106
DEPT (135) NMR Spectrum of Compound 6a.
107
1H and
13C NMR Spectra of Compound 6b.
108
1H and
13C NMR Spectra of Compound 6c.
109
DEPT (135) NMR Spectrum of Compound 6c.
110
1H and
13C NMR Spectra of Compound 11a.
111
DEPT (135) NMR Spectrum of Compound 11a.
112
1H and
13C NMR Spectra of Compound 11b.
113
1H and
13C NMR Spectra of Compound 11c.
114
DEPT (135) NMR Spectrum of Compound 11c.
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